CN211480186U - Metal-air battery positive electrode component with conductive hydrophobic expanded polytetrafluoroethylene membrane - Google Patents
Metal-air battery positive electrode component with conductive hydrophobic expanded polytetrafluoroethylene membrane Download PDFInfo
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- CN211480186U CN211480186U CN202020404766.7U CN202020404766U CN211480186U CN 211480186 U CN211480186 U CN 211480186U CN 202020404766 U CN202020404766 U CN 202020404766U CN 211480186 U CN211480186 U CN 211480186U
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Abstract
The utility model discloses a metal-air battery positive pole part with electrically conductive hydrophobic bulked polytetrafluoroethylene membrane, include: the metal air battery is characterized in that a conductive hydrophobic breathable layer, a metal mesh layer and a catalytic layer are sequentially arranged in the direction of oxygen entering the metal air battery, and the conductive hydrophobic breathable layer is a conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) film. Through the mode, the utility model can not only ensure the good liquid blocking effect of the electrode, but also ensure the effect of oxygen entering the electrode for reaction, so that the positive electrode conductivity of the metal-air battery is better; furthermore, use the utility model discloses the metal-air battery of part is ageing-resistant and corrosion-resistant life-span in the course of the work far exceeds other metal-air battery product life limit.
Description
Technical Field
The utility model relates to a metal-air battery positive pole part with electrically conductive hydrophobic bulked polytetrafluoroethylene membrane.
Background
The metal-air battery has the main characteristics that:
(1) the specific energy is high. Because the active substance used by the air electrode is oxygen in the air, the active substance is inexhaustible, the capacity of the positive electrode is theoretically unlimited, and the active substance is outside the battery, the theoretical specific energy of the air battery is far greater than that of a common metal oxide electrode, the theoretical specific energy of the metal-air battery is generally more than 1000 W.h/kg, the actual specific energy is more than 100 W.h/kg, and the air battery belongs to a high-energy chemical power source. The lower graph shows the performance of a portion of the metal-air cell.
(2) The price is low. The zinc-air battery does not adopt expensive noble metal as an electrode, and the battery materials are common materials, so the zinc-air battery is low in price.
(3) The performance is stable. Especially, after the zinc-air battery adopts the powdery porous zinc electrode and the alkaline electrolyte, the zinc-air battery can work under very high current density, and if pure oxygen is adopted to replace air, the discharge performance can be greatly improved. According to theoretical calculation, the current density can be improved by about 20 times.
The metal-air battery has the following disadvantages. Firstly, the battery cannot be sealed, so that the drying and rising of the electrolyte are easily caused, the capacity and the service life of the battery are influenced, and if the alkaline electrolyte is adopted, the carbonation is easily caused, the internal resistance of the battery is increased, and the discharge is influenced. Second, the wet storage property is poor because diffusion of air in the battery to the negative electrode accelerates self-discharge of the negative electrode. Thirdly, the porous zinc is adopted as the cathode, amalgamation is needed, mercury is harmful to the health of workers and pollutes the environment, and a non-mercury corrosion inhibitor is needed for replacement.
At present, a waterproof breathable layer in the anode of the existing metal-air battery is complex in preparation process, for example, in document CN106910924, PTFE fine powder and conductive powder are mixed in water, an ethanol solvent is added after filtering and drying, and then rolling and heat treatment are carried out to degrade partial high polymers to form macropores; in document CN101831123, PTFE emulsion with a concentration of 60% is mixed with conductive powder, and after drying, a conductive film is prepared by rolling and pressing a film and rolling the film, and the method has complicated filtering and drying operations and poor control of the air permeability of the film; in the document CN110120531, 60% PTFE emulsion is adopted, polyethylene glycol is used as a wetting agent and a pore-forming agent, the filtering and drying operation of the scheme is complicated, and the size of pores is not well controlled. The filtration and drying procedures in the above scheme are complicated, which is not beneficial to large-scale production, and the air permeability of the membrane is not well controlled.
SUMMERY OF THE UTILITY MODEL
The utility model aims to provide a metal air battery positive pole part and preparation method with electrically conductive hydrophobic bulked polytetrafluoroethylene membrane can improve metal air battery's electric conductive property, produces more ions of hydroxyl ion group in equal time at oxygen and water catalytic reaction and produces the formation electric current, the better performance requirement that has satisfied metal air battery electrode of comprehensive properties such as the product is electrically conductive, ventilative, hydrophobic for metal air battery does not have the phenomenon of leaking.
In order to solve the technical problem, the utility model discloses a technical scheme be: provided is a metal-air battery positive electrode member having a conductive hydrophobic expanded polytetrafluoroethylene film, comprising: the metal air battery is characterized in that a conductive hydrophobic breathable layer, a metal net layer and a catalyst layer are sequentially arranged in the direction in which oxygen enters the metal air battery, the oxygen is subjected to chemical reaction on the catalyst layer, the conductive hydrophobic breathable layer, the metal net layer and the catalyst layer are in overlapped adhesive connection, the conductive hydrophobic breathable layer is a conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) membrane, and the pore diameter of a micropore of the membrane is less than 20 mu m.
In a preferred embodiment of the present invention, the conductive hydrophobic expanded polytetrafluoroethylene PTFE membrane has a pore size of less than 20 um.
In a preferred embodiment of the present invention, an electrically conductive hydrophobic air-permeable layer is also disposed between the metal mesh layer and the catalyst layer, and the electrically conductive hydrophobic air-permeable layer is bonded between the metal mesh layer and the catalyst layer.
The utility model has the advantages that: the PTFE membrane in the metal-air battery anode part of the utility model has strong hydrophobicity, does not contain any hydrosolvent in the production process, can permeate oxygen and water vapor, but can not permeate water drops; the electrolyte in the metal-air battery electrode is prevented from leaking outwards, so that the good liquid blocking effect of the electrode can be ensured, the effect of oxygen entering the electrode for reaction can be ensured, and the conductivity of the positive electrode of the metal-air battery is better; furthermore, use the utility model discloses the metal-air battery of part is ageing-resistant and corrosion-resistant life-span in the course of the work far exceeds other metal-air battery product life limit.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention, as generally described and illustrated in the figures herein, may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the accompanying drawings, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "front" and "rear" and the like are based on the directions or positional relationships shown in the drawings, or the directions or positional relationships that the products of the present invention are conventionally placed when used, and are only for convenience of description and simplification of the description, but do not indicate or imply that the device or element to be referred must have a specific direction, be constructed and operated in a specific direction, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used merely to distinguish one description from another, and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should also be noted that, unless otherwise explicitly specified or limited, the terms "disposed" and "connected" are to be interpreted broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In the present disclosure, unless otherwise expressly stated or limited, the first feature may comprise both the first and second features directly contacting each other, and also may comprise the first and second features not being directly contacting each other but being in contact with each other by means of further features between them. Also, the first feature being above, on or above the second feature includes the first feature being directly above and obliquely above the second feature, or merely means that the first feature is at a higher level than the second feature. A first feature that underlies, and underlies a second feature includes a first feature that is directly under and obliquely under a second feature, or simply means that the first feature is at a lesser level than the second feature.
Fig. 1 is a schematic structural view of a preferred embodiment of the positive electrode member of a metal-air battery of the present invention having a conductive hydrophobic expanded polytetrafluoroethylene film;
fig. 2 is a process flow diagram of the preparation method of the middle conductive hydrophobic bulked polytetrafluoroethylene membrane of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.
The embodiment of the utility model provides an include:
a metal-air cell positive electrode member having a conductive hydrophobic expanded polytetrafluoroethylene membrane, comprising: the metal-air battery is sequentially provided with a conductive hydrophobic breathable layer 6, a metal mesh layer 7 and a catalytic layer 8 along the direction A of oxygen entering the metal-air battery, oxygen is subjected to chemical reaction on the catalytic layer 8, and oxygen is subjected to chemical reaction O2+2H2O+4e=4OH-And the conductive hydrophobic breathable layer 6, the metal mesh layer 7 and the catalytic layer 8 are connected in a superposed adhesive manner through conductive glue.
As shown in fig. 1, in the present invention, an electrically conductive hydrophobic air-permeable layer 6 is also preferably disposed between the metal mesh layer 7 and the catalytic layer 8, and the electrically conductive hydrophobic air-permeable layer 6 is bonded between the metal mesh layer 7 and the catalytic layer 8.
The conductive hydrophobic breathable layer 6 is a conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) membrane, and the aperture of the micropores of the membrane is less than 20 mu m.
The diameter of the water vapor (single water molecule) is 0.4 nm; the water drops are aggregated water molecules, and the diameter of the water drops is larger than 100 um; the molecular diameter of oxygen is 0.346 nm; from the data, the PTFE film can permeate oxygen and water vapor but cannot permeate water drops, so that the electrolyte inside the metal-air battery electrode is prevented from leaking outwards, and oxygen can be ensured to enter the electrode for reaction.
The utility model discloses still relate to a preparation method of metal air battery positive pole part with electrically conductive hydrophobic inflation polytetrafluoroethylene membrane, including following step:
1) preparing a catalyst layer, a conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) film, conductive glue and a metal or alloy mesh plate;
2) printing or spot-coating uniformly distributed conductive glue on the bonding surface of the conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) film and the metal or alloy mesh plate, and superposing;
3) and (5) compacting, curing and bonding, wherein the pressure intensity of the compacting, curing and bonding is 0.01-0.3 Mpa, and finally, the component is prepared after the qualified inspection.
The preparation method of the conductive hydrophobic expanded polytetrafluoroethylene PTFE membrane comprises the following embodiments:
example 1:
an electrically conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) membrane comprising: 50wt% -70 wt% of polytetrafluoroethylene PTFE material and 30wt% -50 wt% of carbon.
The carbon comprises a mixture of one or more of carbon black, graphene, carbon nanotubes and carbon fibers.
The utility model discloses select for use polytetrafluoroethylene PTFE material as the substrate, polytetrafluoroethylene PTFE material can be forms such as emulsion, powder, granule.
A method for preparing a conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) membrane, as shown in fig. 2, comprises the following steps:
1) putting polytetrafluoroethylene PTFE fine powder and carbon into a transparent container with the specification of 60cm multiplied by 80cm, uniformly mixing, slowly adding 1100ml of lubricant, and uniformly mixing again, wherein the lubricant is one or more of kerosene, alkane and ethanol;
2) and (3) extruding the uniformly mixed powder 1 into strips through a small opening die 2, wherein the maximum extrusion pressure is 15-20 MPa, and then performing double-roller calendering 3, wherein the minimum distance between rollers of the double-roller calendering 3 is 0.03-0.05 mm.
3) And (3) carrying out high-temperature heating 4 after rolling, wherein the average temperature of a heating drying tunnel is 200-250 ℃ to remove the lubricant in the product and remove stress, and finally carrying out rolling, wherein the normal rolling speed of a rolling machine 5 is 6-10 rpm, so that oriented stretching is realized, the microporous structure of the film is formed, the size of micropores can be adjusted at will, and the preparation of the conductive hydrophobic expanded polytetrafluoroethylene PTFE film is finished.
Example 2: an electrically conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) membrane comprising: 60-80 wt% of polytetrafluoroethylene PTFE material and 20-40 wt% of pure metal powder.
The metal powder includes a mixed powder of one or more of nickel, copper, and silver.
The utility model discloses select for use polytetrafluoroethylene PTFE material as the substrate, polytetrafluoroethylene PTFE material can be forms such as emulsion, powder, granule.
A method for preparing a conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) membrane, as shown in fig. 2, comprises the following steps:
1) putting polytetrafluoroethylene PTFE fine powder and metal powder into a transparent container with the specification of 60cm multiplied by 80cm, uniformly mixing, slowly adding 800ml of lubricant, and uniformly mixing again, wherein the lubricant is one or more of kerosene, alkane and ethanol;
2) and (3) extruding the uniformly mixed powder 1 into strips through a small opening die 2, wherein the maximum extrusion pressure is 15-20 MPa, and then performing double-roller calendering 3, wherein the minimum distance between rollers of the double-roller calendering 3 is 0.03-0.05 mm.
3) And (3) carrying out high-temperature heating 4 after rolling, wherein the average temperature of a heating drying tunnel is 200-250 ℃ to remove the lubricant in the product and remove stress, and finally carrying out rolling, wherein the normal rolling speed of a rolling machine 5 is 6-10 rpm, so that oriented stretching is realized, the microporous structure of the film is formed, the size of micropores can be adjusted at will, and the preparation of the conductive hydrophobic expanded polytetrafluoroethylene PTFE film is finished.
Example 3: an electrically conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) membrane comprising: 65-85 wt% of polytetrafluoroethylene PTFE material and 15-35 wt% of nickel-coated carbon.
The nickel-coated carbon can be one or two mixtures of nickel-coated graphite and/or nickel-coated carbon fiber.
The utility model discloses select for use polytetrafluoroethylene PTFE material as the substrate, polytetrafluoroethylene PTFE material can be forms such as emulsion, powder, granule.
A method for preparing a conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) membrane, as shown in fig. 2, comprises the following steps:
1) putting polytetrafluoroethylene PTFE fine powder and nickel-coated carbon into a transparent container with the specification of 60cm multiplied by 80cm, uniformly mixing, slowly adding 950ml of lubricant, and uniformly mixing again, wherein the lubricant is one or more of kerosene, alkane and ethanol;
2) and (3) extruding the uniformly mixed powder 1 into strips through a small opening die 2, wherein the maximum extrusion pressure is 15-20 MPa, and then performing double-roller calendering 3, wherein the minimum distance between rollers of the double-roller calendering 3 is 0.03-0.05 mm.
3) And (3) carrying out high-temperature heating 4 after rolling, wherein the average temperature of a heating drying tunnel is 200-250 ℃ to remove the lubricant in the product and remove stress, and finally carrying out rolling, wherein the normal rolling speed of a rolling machine 5 is 6-10 rpm, so that oriented stretching is realized, the microporous structure of the film is formed, the size of micropores can be adjusted at will, and the preparation of the conductive hydrophobic expanded polytetrafluoroethylene PTFE film is finished.
Example 4: an electrically conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) membrane comprising: 60-75 wt% of polytetrafluoroethylene PTFE material and 25-45 wt% of ferrite magnetic material.
Ferrites are divided into soft magnetic ferrites and permanent magnetic ferrites.
The soft magnetic ferrite comprises ferrite consisting of one or more of manganese ferrite (MnO. Fe2O3), zinc ferrite (ZnO. Fe2O3), nickel zinc ferrite (Ni-Zn. Fe2O4) and manganese magnesium zinc ferrite (Mn-Mg-Zn. Fe2O 4).
The permanent magnetic ferrite comprises barium ferrite (BaO & 6Fe2O3) or/and strontium ferrite (SrO & 6Fe2O 3).
The utility model discloses select for use polytetrafluoroethylene PTFE material as the substrate, polytetrafluoroethylene PTFE material can be forms such as emulsion, powder, granule.
A method for preparing a conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) membrane, as shown in fig. 2, comprises the following steps:
1) putting polytetrafluoroethylene PTFE fine powder and ferrite into a transparent container with the specification of 60cm multiplied by 80cm, uniformly mixing, slowly adding 1000ml of lubricant, and uniformly mixing again, wherein the lubricant is one or more of kerosene, alkane and ethanol;
2) and (3) extruding the uniformly mixed powder 1 into strips through a small opening die 2, wherein the maximum extrusion pressure is 15-20 MPa, and then performing double-roller calendering 3, wherein the minimum distance between rollers of the double-roller calendering 3 is 0.03-0.05 mm.
3) And (3) carrying out high-temperature heating 4 after rolling, wherein the average temperature of a heating drying tunnel is 200-250 ℃ to remove the lubricant in the product and remove stress, and finally carrying out rolling, wherein the normal rolling speed of a rolling machine 5 is 6-10 rpm, so that oriented stretching is realized, the microporous structure of the film is formed, the size of micropores can be adjusted at will, and the preparation of the conductive hydrophobic expanded polytetrafluoroethylene PTFE film is finished.
The volume resistivity of examples 1-4 was measured by the four-probe method, and the shielding effectiveness of examples 1-3 was measured coaxially with a flange, and the results were as follows:
| content of test | Thickness of | Volume resistivity | Shielding effectiveness |
| Example 1 | 1.0mm | 1.5Ω·cm | 23dB |
| Example 2 | 1.0mm | 23.6Ω·cm | 12dB |
| Example 3 | 1.0mm | 12.9Ω·cm | 18dB |
| Example 4 | 1.0mm | 9.4Ω·cm | 15dB |
In conclusion, the conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) film has excellent performance: the cable is resistant to high and low temperatures (-60-260 ℃), corrosion-resistant, ultraviolet-resistant and non-discoloring for 20 years, can meet the requirement that the device or facility can be normally used in severe environmental conditions such as low temperature, high humidity, high salt and oil-water pollution comprehensive application occasions (islands, ships and deserts), and can reliably prevent electromagnetic signal interference and leakage; the preparation method is also beneficial to large-scale production, and meanwhile, the product has good flatness, high strength and good shielding efficiency.
When the polytetrafluoroethylene PTFE membrane with the conductive hydrophobic expansion is applied to the metal-air battery anode part, the hydrophobicity is strong, and no water solvent exists in the production process, so that oxygen and water vapor can permeate through the membrane, but water drops cannot permeate through the membrane; the electrolyte in the metal-air battery electrode is prevented from leaking outwards, so that the good liquid blocking effect of the electrode can be ensured, the effect of oxygen entering the electrode for reaction can be ensured, and the conductivity of the positive electrode of the metal-air battery is better; furthermore, use the utility model discloses the metal-air battery of part is ageing-resistant and corrosion-resistant life-span in the course of the work far exceeds other metal-air battery product life limit.
The above only is the embodiment of the present invention, not limiting the patent scope of the present invention, all of which utilize the equivalent structure or equivalent flow transformation made by the content of the specification of the present invention, or directly or indirectly applied to other related technical fields, all included in the same way in the patent protection scope of the present invention.
Claims (3)
1. A metal-air battery positive electrode member having a conductive hydrophobic expanded polytetrafluoroethylene membrane, characterized by comprising: the metal air battery is characterized in that a conductive hydrophobic breathable layer, a metal mesh layer and a catalytic layer are sequentially arranged in the direction of oxygen entering the metal air battery, oxygen is subjected to chemical reaction on the catalytic layer, the conductive hydrophobic breathable layer, the metal mesh layer and the catalytic layer are in overlapped adhesive connection, and the conductive hydrophobic breathable layer is a conductive hydrophobic expanded Polytetrafluoroethylene (PTFE) film.
2. The metal-air battery positive electrode member with the conductive hydrophobic expanded polytetrafluoroethylene membrane according to claim 1, wherein the conductive hydrophobic expanded polytetrafluoroethylene PTFE membrane has a pore size of < 20 um.
3. The metal-air battery positive electrode component with the conductive hydrophobic bulked polytetrafluoroethylene membrane according to claim 1, wherein a conductive hydrophobic air-permeable layer is also arranged between the metal mesh layer and the catalytic layer, and the conductive hydrophobic air-permeable layer is adhered between the metal mesh layer and the catalytic layer.
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